Oxygen treated organic products and methods for producing them



Patented Feb. 4, 1947 UNITED STATES PATENT-O FFICE AND METHODS FORPRODUCING THEM Mortimer-T. Harvey, South Orange, N. .L, assignmto HarvelResearch Corporation, a corporation I of New Jersey No Drawing.Application April 26,1944,

. Serial No. 532,884

14 Claims. (Cl. 260-606) This invention relates to novel products and tomethods for preparing the same. In one of its specific aspectsthisinvention is directed to novel products capable of producing gelswith certain compounds and to the methods for producing said products.In another aspect this organic substances in their unoxidized condition.

invention relates to gels and millable and cured compositions and to themethods for producing said gels and millable and cured compositions.

This application isa continuation in part of my copending applicationSerial No. 405,074, med August 1, 1941,

I have produced gels which comprised a norwood oil, cedrene, etc. withformaldehyde in the presence of an acidic condensing agent (examples ofsome of said terpene-formaldehyde liquid reaction products are disclosedin my Patent 2,350,230 issued May 30,1944) the liduid condensationreaction productsof a terpene alcohol, examples of which are pine oil,terpineol,

eucalyptol, etc., with formaldehyde in the presence of an acidiccondensing agent (examples of some of said terpenealcohol-formaldehyde-reraction products are disclosed in my Patent Someof said are oxygen, air, ozone, and the like.

Said substances of said class may be oxidized to increase the percentageof combined oxygen. therein and to increase their viscosities bysubiecting the same to an oxidizing agent capable of e V so modifyingsaid substances. Among some of the agents which may be used for-thispurpose The invention-is particularly directed to the treatment of thatclass of normally liquid unsaturated organic products which when in theratio of 5 parts of anyone of said products to one part of normallysolid polyvinyl chloride can be heated to an elevated temperature ofabout 250 F. to-350 F. to form a solution'whichupon cooling is a gel atF. The invention also is directed to the resultant products produced byfollowing the methods of this inventiornwhich resultant products whichwhen'in the ratio of five parts of any one of said products to one partof normally solid polyvinyl chloride can be heated to an elevatedtemperature of about 250 F. to 350 F, to form a solution which uponcool-.

ing' is a gel at 70 F.

One of the commercially practical methods which may be employed inoxidizing said substances of said class is to-blow the samewith oxygen,ozone or air. Briefly stated, the novel method comprises heating aboveabout F. a" mass of ,a normally liquid unsaturated organic productcapable at elevated ;temperatures of forming a solution with solidpolyvinyl chloride which solution on coolingis a. gel at 70F. and whilesaid mass is in said heated condition agitating said massin the presenceof ages containing free oxygen .until the viscosity of said mass at 25C. has increased-atleast 0.5%. A1-

2,362,538 issued November 14, 1944) and the nor-,

mally liquid condensation reaction products-of tertiary alkylalcohols,;- examples of which are, tertiary amyl alcohol, tertiary butylalcohol, tertiary hexyl alcoh tertiary heptyl alcphol, tertiary octylalcoho etc., with formaldehyde in the presence of an acidic condensingagent.

Accordingto the present invention, novel prod- I ucts are obtainedby'oxidizing that class of normally liquid unsaturated organicsubstances which are capable of forming .a gel with said normally solidpolymers and copolymers of the vinyl compounds heretofore set forth.These novel oxidized productsare characterizedby a greater viscosity andgreater percentage of combined oxygen content when comparedwith thecorresponding characteristics. of said unsaturated though temperaturesgreatly in excess of 140 F. maybe employed,- Iprefer to employ atemperature. range ofvbetween about 140 F. to 400 F.notwithstanding'that temperatures in excess of 400 F; and as high as 60025'. may beemployed. While ,a wide variety of gas containing free oxygenmay be employed, forthfe purposes of illustration, I disclose the-use oiair, oxygen or ozone, the former. being thelmost preferable because ofitsjavailabilityand low cost. The agitation of said normallyliquidunsaturated organic product may be accomplished by flowing the material,by projecting the material, or'by forcing the gas itself through thematerial being treated.

One of the specific methods for producing these novel products whichmethod is particularly applicable commerciallyis to blow said normallyliquid unsaturated organic product at temtion takes place at saidtemperature.

3 peratures above 140 F. with a gas containing free oxygen. The blowingmay be carried out by forcing said gas through the heated product beingtreated, by allowing the product being treated to trickle over inclinedsurfaces in the presence of said gas, or by forcing the product beingtreated through an "atomizing" nozzle to break the same into smallparticles which are projected into a chamber containing said gas. Anyone of said specific methods may be employed alone or a combination oftwo or more of them may be used. This invention may be practiced atatmospheric pressure or super atmospheric pressures. These specificmethods are set forth merely for the-purposes of illustration and showthat variations of these particular methods may be used to obtainagitation and therefore a high degree of surface contact of the productbeing treated to said gas so that the time of treatment may be such asto make the process commercially practicable. While the time oftreatment is variable, depending on the temperature of the product beingtreated and the degree of surface contact of this product and said gasper unit of time, I prefer that the product being treated be maintainedabove 140 F. and a contact with the free oxygen containing gas until theviscosity at 25 C. of the resultant product be at least 50% greater thanthe viscosity at 25 C. of the untreated product and that its percentageof combined oxygen be at least 0.5% greater than the percentage ofcombined oxygen of the untreated product. In most cases, however, Iprefer that this treatment be continued until the resultant product hasa viscosity which is at least 100% greater than that of the untreatedproduct and its combined oxygen content be at least 100% greater thanthat of the untreated product.

The alkyl esters of abietic acid and preferably the alkyl esters ofabletic acid having from one to four carbon atoms in the alkyl grouprepresent one genus of a normally liquid unsaturated organic materialwhich is capable at elevated temperatures of forming a solution withsolid polymers of vinyl chloride, vinyl acetate, vinyl chloracetate, andthe vinyl acetals, such as vinyl butyral, etc., and copolymers of vinylchloride and vinyl acetate which solution upon cooling is a gel at 70 F.A wide variety of gels may be produced by varying the ratio of thequantity of the ester employed to the quantity of the polymer orcopolymer employed. For the purposes of illustration, the following is aspecific example of the method for producing a gel which is a rubberymass.

Example 1.--One hundred parts by weight of methyl abietate, hereinafterreferred to as product L, are heated to between 150 C. and 165 C andtwenty-five parts of solid polymerized vinyl chloride, known to thetrade as "vinylite QYNA,

having a molecular weight of about 20,000 to 22,000, are added to saidmethyl abietate at said temperature and the mass is stirred until solu-The solution is allowed to cool to room temperature and at thistemperature of about 70 F. this mass is a gel which may be furthercharacterized as rubbery and resilient. The methyl abietate em ployed isobtainable on the market as Abalyn and has a specific gravity at 25 C.of 1.025 and a viscosity at 25 C. of 3200 centipoises. Although methylabietate has been employed in this example the other alkyl esters ofabietic acid and particularly those having from one to four carbon atomsin the alkyl group may be substituted i for the methyl abietate and maybe of the same quantity by weight to obtain the same type solid rubberygel.

A second genus of a normally liquid unsatu- 5 rated organic materialcapable at elevated temperatures of forming a solution with a solidresin selected from the group consisting of polymers of vinyl chloride,vinyl acetate, vinyl chloracetate, and the vinyl acetals such as vinylbutyral, etc., and copolymers of vinyl chloride and vinyl acetate arethe liquid organic condensation reaction products produced by reacting aterpene with formaldehyde in the presence of an acidic catalyst.

A commercially practical method for producing this second genus is toreact a terpene and formaldehyde in aqueous solution in the presence ofan amount of an acid so limited in quantity that the pH of the aqueousphase of the mix is less than that required to cause material polymerization of the terpene. In carrying out this process, between 1 to 7molecular proportions and preferably between 3 to 7molecularproportionsof formaldehyde are used for each molecularproportion of the terpene. The commercially available aqueous solutionof formaldehyde containing approximately 37.5-40% formaldehyde isemployed. The quantity of acid is preferably a very low and for mostpurposes may be between 0 .01 and 0.1 mole per mole of terpene.

The following Examples 2-7 inclusive, illustrate the specific manner ofpreparing some of said reaction products of this genus and are given forthe purposes of illustration.

Example 2.-About 150 pounds of a commercial water solution offormaldehyde (about 37.5% formaldehyde in water), .about 100 pounds ofgum turpentine (U. S. Naval Stores) and about 250 cc. of concentratedsulphuric acid were placed together and agitated, the formaldehydesolution and the sulphuric acid being brought; carefully together beforethe turpentine was added. This mixture of turpentine, formaldehydesolution and sulphuric acid were heated to boiling and maintained in thestate of boiling under a reflux condenser while being constantlyagitated for about nine hours. At the end of this nine hour period about2.25 pounds of dry caustic soda was added to the resulting mix andagitated 50 therein for about an hour in orderto neutralize thesulphuric acid present. The mixture was allowed to stand for about 8hours after which it was found to have separated into two main layers,(a) an oily or oil-like layer and (b) a watery layer. The oily oroil-like layer was separated from the water layer and placed in pans inan over 'at about 275 F. to vaporize and remove any remaining water anduntil a practically clear solution of the condensation reaction productwas 60 obtained in a solvent such as ethyl alcohol. This oily oroil-like product thus finally obtained is hereinafter designated asproduct A, at 27 C. has a specific gravity of 1.08 and at 25 C. has aviscosity of 6156 centipoises.

Example 3.--About 40 pounds of 37.5% formaldehyde in water solution,about 57 pounds of .pinene and about 120 cc. of concentrated sulphuricacid were mixed together, the formaldehyde solution and sulphuric acidhaving been 70 carefully brought together before the turpentine wasadded. This mixture of aqueous formaldehyde solution, turpentine andsulphuric acid was heated to boiling and maintained in this state ofboiling under a reflux condenser while being con- 75 stantly agitatedfor about nine hours. At the end therethrough to neutralize thesulphuric acid.

The mixture was allowed to stand for about 8 hours after which it wasfound to have separated into two main layers, (a) an oily or. oillikelayer and (b) a watery layer. The oily or oil-like layer was separatedfrom the water layer and placed in pans in an oven at 275 1'. to removeany remaining water and until a practically clear solution of the samemay be obtained in a solvent such as ethyl alcohol. This oily or oillikeproduct thus finally obtained is hereinafter designed as product B.

Example 4.About 900 grams of aqueous solution of formaldehyde (37.5%formaldehyde in water), were mixed with about-i cc. of concentratedsulphuric acid. Then to said mixture was added about 544 grams ofdipentene. This mixture of formaldehyde solution, sulphuric acid anddipentene was hea ed to boiling and ma ntained in this state of boilingunder a reflux condenser and while being constantly agitated for aboutsix hours. At the end of this six hour period, about 4.3 grams of drycaustic soda was added to the resulting mix and this mixture was heatedto boiling for about one more hour and then allowed to cool to aboutroom temperature whereupon the mixture was two separate layers, (a) anoily or oil-like layer and (b) a watery layer. The oily or oil-likelayer was separated from the watery layer and dehydrated as set forth inExamples 2 and 3. The resultant oily or oil-like layer of this exampleis hereinafter designated as product C, at 32 C.'has a specific gravityof 0.971 and at 25 C. has a viscosity of 19 centipoises.

Example 5.About 675 grams of an aqueous solution of formaldehydecontaining 37.5% formaldehyde and 3.5 cc. of concentrated sulphuric acidwere mixed together and 560 grams of cedar wood oil added thereto. Thismixture of formaldehyde solution, sulphuric acid and cedar wood oil washeated to 'boiling and maintained in this state of boiling under areflux condenser while being continuously agitated for a period of about9 hours. Thereafter, 3.6 grams of dry caustic soda were added theretoand admixed therewith to neutralize the sulphuric acid. The mixture wasallowed to stand after which it was separated into two main layers (a)an oily or oil-like layer and (b) a watery layer. The oily or oil-likelayer was separated from the watery layer and placed in pans in an ovenat 275 F. to remove any remaining water. This oil-like product thusfinally obtained is hereinafter designated as product D, and has at 25C. a specific gravity of 0.972 and a viscosity of 43.7.

Instead of employing an aqueous solution of formaldehyde in thepreparation of the reaction condensation products of terpenes andformaldehyde, the reaction may be carried out with substantiallyanhydrous reactants, and even in this instance the quantity of mineralacid catalyst employed is less than that required to cause appreciablepolymerization of the terpenes. The following illustrates the manner ofpreparing some of the reaction products of said second genus under saidconditions:

Example 6.-A mixture of 462 parts of turpentine, 90 parts ofparaformaldehyde, 30 parts of glacial acetic acid and 3.3 parts ofconcentrated sulphuric acid is heated to boiling and maintained in thisstate of boiling while being constantly agitated for about eight hoursunder a reflux condenser. The resultant mass is neutralized by addingand admixing therewith caustic soda after which salts precipitate outand may be removed by decantation. The liquid 5 may then be distilled todistill on the water,

acetic acid, as well as any unreacted formaldehyde and turpentine. Theremaining liquid is the organic condensation reaction product, willhereinafterbe designated as product E and has 1 .at 25 C. a specificgravity of 1.09 and a viscosity of 5300 centipoises. Example 7.- Amixture of 350 parts of pinene, 90 parts of paraformaldehyde, 30 partsof glacial acetic acid and 3.3 parts of concentrated sulphuric acid isheated to boiling and maintained in this state while being constantlyagitated for about 8 hours under a reflux condenser. The resultant massis then neutralized by admixing therewith caustic soda after which saltsprecipitate out and are removed therefrom. The liquid may then bedistilled to drive on the water, acetic acid, as well as any unreactedpinene and :formaldehyde. The remaining liquid is the organiccondensation reaction product, will hereinafter be designated as productF. and has at 25 C. a specific gravity of 1.08 and a viscosity of 570centipoises.

A third genus of a normally liquid unsaturated organic material capableat elevated temperatures of forming a solution with a solid resinselected from the group consisting of polymers and copolymers of vinylchloride, vinyl acetate, vinyl chloracetate and the vinyl acetals, suchas vinyl butyral, etc., are the liquid organic condensation reactionproducts produced by reacting a terpene alcohol with formaldehyde in thepresence of an acidic catalyst.

A commercially practical method for producing this third genus is toreact a terpene alcohol and formaldehyde in aqueous solution in thepresence of an amount of an acid so limited in quantity that the pH ofthe aqueous phase of the mix is less than that required to causeappreciable polymerization of the terpene alcohol. In 45 carrying outthis process. between 1 and 7 molecular proportions and preferablybetween 2 and 7 molecular proportions of formaldehyde are used for eachmolecular proportion of the terpene alcohol. Commercially availableaqueous solution of formaldehyde containing 37.5 to 40% formaldehyde isemployed. The quantity of acid is preferably very low and for mostpurposes the mole ratio of the formaldehyde to the acid catalyst in saidmixture may be between about 3 to .01

55 and 1. to .1.

The following examples ,8-10 illustrate the specific manner of preparingsome of the reaction products of this genus and are given for thepurposes of illustration:

0 Example 8.--About 612 grams of an aqueous solution of formaldehydecontaining 37.5% formaldehyde and 3.1 cc. of concentrated sulphuric acidwere mixed together and 375 grams of pine oil were added thereto. Thismixture of pine oil, sulphuric acid and aqueous formaldehyde was heatedto boiling and maintained in this state of boiling under constantagitation and under a reflux condenser for about six hours. Then about4.3 grams of dry caustic soda was added thereto and admixedtherewithtoneutralize the sulphuric acid. At room temperature, the mixseparated into two main layers, (a) an oily or oil-like layer and (b) a,water layer. The oily or oil-like layer was dehydrated by heating as inExamples 2 and 3 to provide reaction condensation product hereablyemployed for this purpose is to blow said substances with air, oxygen,ozone or the like. The blowing may be accomplished by forcing said air,oxygen, ozqne or the like through a quantity of said substance in atank, or by spraying or flowing said substances into or through anambient of ozone, air or oxygen. In carrying out this operation, it ispreferable that the substance being blown be maintained between about160 F. to about 200 F. and the temperature of the air, oxygen or ozonebe at least as high as room temperature although it may. also be at theelevated temperature employed. i

The following is an illustrative general exampie for increasing theviscosity and combined oxygen content of said unsaturated organicliquids capable of dissolving said vinyl resins and forming a geltherewith.

Example 14.A quantity of one of said unsaturated organic liquids, suchas any one 01 the specific products A-L, is placed into a closedeontainer having a, conduit extending through the top thereof andterminating at a point spaced from but near the bottom thereof. Thelower end of said conduit has a plurality of lateral openingstherethrough, through which air, oxygen or ozone may be discharged andinto said unsaturated organic liquid at places below the upper surfacesof said liquid. The container has a vent located near the top thereof torelease air, used to prevent too great pressure being built up in saidcontainer and to allow the air, oxygen or ozone to circulate throughsaid liquid. A stirrer is employed to constantly agitate said liquidthroughout the entire operation thereby to in-. crease the contact ofthe liquid with the air, oxygen or ozone. Throughout the entireoperation, the liquid is maintained at a temperature between about 160F. and 300 F., while the air, oxygen or ozone, admitted to saidcontainer may be at room temperature. The quantity of liquid in thecontainer may be about one-quarter of the capacity thereof in order toaccommodate the great deal of splashing due to the bubbling of the air,oxygen or ozone therethrough and the agitation due to stirring. After aperiod of between about 24 to 144 hours, depending upon the rate ofstirring, the rate of air, oxygen or ozone admission and the quantity ofsaid liquid, said liquid will be found to have increased in specificgravity, viscosity and combined oxygen content when compared with therespective corresponding characteristics before said operation wasbegun. The combined oxygen content will have increased at least 1% andin some cases will have increased as high as about 19% or more. Theviscosity at 25 C. will have increased at least 100% and in some caseswill have increased to Example 16.--After product was heated to atemperature of about 90 C. and air blown for aperiod of 72 hours whilebeing maintained at said elevated temperature, the resulting productheresuch a degree that it has been converted to a,

mass which is semi-solid at 25 0.

Example 15.After products A, D, G and H were heated to a temperature ofabout 90 C. and air blown for a period of 24 hours while beingmaintained at said elevated temperature, the resulting respectiveproducts, hereinafter designated A0, D0, G0 and H0 had the followingspecific gravities and viscosities:

inafter designated as CO had at 25 C. a specific gravity of 0.988 and at25 C. a viscosity of 60 centipoises.

Example 17.-After products E, F and I are heated to an elevatedtemperature of about C. and air blown for a period of about 6 hours,

while being maintained at said elevated temperature, the resultingrespective products, hereinafter designated as E0, E0 and 10 will allhave been converted to a semi-solid state and all will have increased incombined oxygen content by more than 1%. Product E0 will be found tohave had a high percentage increase in combined oxygen content which isover 19%.

Example 18.After product M is heated to an elevated temperature of 90 C.and air blown for a period of 24 hours while being maintained at saidelevated temperature the resulting product, hereinafter designated as M0will have become converted from a liquid to a semi-solid and itscombined oxygen content will have been increased by more than 2%.

Example 19.After productK is heated to an elevated temperature of about90 C. and air blown for a period of about 30 hours while beingmaintained at said elevated temperature, the resulting producthereinafter designated as K0 will hav at 25 C. a viscosity of 600centipoises and will have more than 1% increase in combined oxygencontent.

Besides these characteristics of greater combined oxygen content, higherspecific gravity and viscosity, these oxidized products, of whichproducts A0, C0, D0, E0, E0, GO, H0, 10, K0 and M0 are examples haveenhanced solubility characteristics for said vinyl resins and are morereadily dissolved by solid rubbery polymers of chloroprene butadiene,solid rubbery copolymers of butadiene and styrene and of butadiene andacrylonitrile and by natural and reclaimed rubber, with all of whichthey act enhanced as plasticizers, These oxidized products, in addition,are useful in the art generally and are useful particularly, forexample, (1) for putting vegetable oils into solution with cellulosenitrate, (2) as solvents for materials such as resins of theglycerol-aldehyde resins, vegetable oils, cellulose nitrate, celluloseacetate and ethyl cellulose, (3) flotation of ores, (4) aiding thesolvent properties of soaps, and (5) insecticidal sprays when employedeither alone or in combination with solids or in a water-soap suspensionconsisting of about 200 parts of any one of said oxidized products inabout parts of water and about parts of sodium oleate. This is thendiluted by about 25-50 times its weight with water and used as a spray.

Improved gels are obtained by employing (a) the polymers of vinylchloride, vinyl acetate, vinyl chloracetate and vinyl acetals, such asvinyl butyral, etc., as well as the copolymers of vinyl chloride andvinyl acetate, especially those polymers and copolymers having amolecular weight of above about 20,000 and in those cases where overwide limits depending upon the type of gel desired, Generally thestiffness or the rigidity of the gel may be controlled by varying thisratio, and the stiffness and rigidity characteristic is directlyproportional to this ratio, 1. e., the higher this ratio, the stiffervand more rigid the gel. Thus very rigid and stiff solid compositions ofmatter as well as soft and pliant solid compositions of matter may beproduced; solid rubberlike resilient gels may be produced in this man--ner by employing between about one to twentyfive parts of one of saidoxidized productsto each part of said vinyl resin. In some cases, andparticularly in those cases, where the oxidized product is still aliquid, the same may be subjected to distillation in order to drive offsome or all those fractions having boiling points below a predeterminedtemperature before the oxidized product is mixed with the vinyl resin sothat after a solution, theresultant gel at room temperature hasparticular characteristics of dryness, tackiness or wetness desired.,For example blown or oxidized Abalyn, product M0, was heated up toabout240 C. to remove about 10% of its weight and product 00 was heatedto remove 20% of its weight and in each case they gave a dry gel-likeproduct after solution with V'YNW, solid copolymer of vinyl chloride andvinyl acetate when the ratio of product M0 or C0 to the solid resin was5 to 1.

The following are specific examples of specific gels which may beproduced as well as the methods which may be employed for the productionof these gels, all of the parts being given by weight.

Example 20.About 100 parts of M0 are mixed with about 25 parts of solidpolymerized vinyl chloride, known to the trade as "Vinylite QYNA, havinga molecular weight above 20,000. This mixture is heated in order toraise the temperature thereof to between about 150 C. and 165 C. and ismaintained at this temperature and is constantly stirred or agitated toprovide a solution thereof. Then the solution is allowed to cool to roomtemperature 70 F. and at said temperature is a rubbery mass and is agel.

Example 21.-About 2 parts of A0 are mixed with about 1 part of solidpolyvinyl acetate, known to the trade as Vinylite AYAT." This mixture isheated toraise the temperature of the mix to between about 290 F. and320 F. and is maintained at thi temperature and is constantly stirred oragitated to provide a solution thereof. Then the solution is allowed tocool to room temperature, 70 F. and at this temperature is a gel and isa rubbery mass.

Example 22.About 3 parts of IO are mixed with about 1 part of a solidcopolymer of vinyl acetate and vinyl chloride, such as VYNF which is asolid copolymer of eighty-seven parts of vinyl chloride and thirteenparts of vinyl acetate or VYNS which is a solid copolymer of ninety partof vinyl chloride and ten parts of tion thereof.

' 12 vinyl acetate. This mixture is heated to between about 290 F. and320 F. and is maintained at this temperature while being constantlystirred to provide a solution thereof. Then the solution is allowed tocool and at room temperature, 70 F., is a gel and a rubbery mass.

Example 23.-About 3 parts of F0 are mixed with about 1 part of a solidpolyvinyl acetal, such as polyvinyl butyral, known on the market asXYFG, and prepared by treating polyvinyl alcohol with butyric aldehyde.This mixture of F0 and polyvinyl butyral is heated to a temperature ofbetween about 290 F. to about 320 F. while being stirred to provide asolution thereof. Then the solution is allowed to cool to roomtemperature, 70 F., and is a gel and a rubbery mass.

Example 24.About 25 parts of E0 are mixed with about 1 part of solidpolyvinyl chloride. This mixture is heated to between about 290 F. and320 F. and maintained at this temperature while being constantly stirredto provide a solution thereof. Then the solution is allowed to cool toroom temperature, 70 F., and at said temperature is a rubbery mass and agel.

Example 25.About 4 parts of K0 are mixed with about 1 part of solidpolyvinyl chloride. This mixture is heated to between about 290 F. and320 F. and maintained at this temperature while being constantlyagitated to provide a solu- Then the solution is allowed to cool to roomtemperature, 70 F., and at said temperature is a rubbery mass and a gel.

Novel and improved millable compositions and cured compositions areprovided by employing the combination of (a) a rubbery substanceselected from the group consisting of solid, rubbery polymers ofchlorbutadiene, solid rubbery polymers of butadiene. solid rubberycopolymers of butadiene and styrene, solid rubbery copolymers ofbutadiene and acrylonitrile, natural rubber and reclaimed rubber and (b)a gel comprising a normally solid vinyl resin selected from the groupconsisting of the polymers of vinyl chloride, vinyl acetate, vinylchloracetate and vinyl acetals, such-as vinyl butyral, and copolymers ofvinyl chloride and vinyl acetate and the oxidized product of a normallyliquid unsaturatthat the ratio of the quantity of said rubbery substanceby weight to quantity by weight of the resin in said gel is betweenabout 50 to 1 and 2 to 1. Millable compositions having improved tearresistance properties may be produced by mixing a quantity of (a)together with a quantity of (b) on a rubber mill. The following generalexample is illustrative of this phase of the invention.

Example 26.--A quantity of a rubbery substance of the aforesaid (a)class was gradually added to a quantity of a gel of the aforesaid (b)class while the latter was being masticated on a differential speed rollmill, the rolls of which were maintained at a temperature approximatelyabout F; Milling is continued until there is forcing materials as wellas other material used in the compounding of rubber may be added to saidmixture and dispersed therethrough on said rubber mill. This product isthen sheeted and cured in the usual manner.

Since certain changes in carrying out the above process and certainmodifications in the compositions which embody the invention may be madewithout departing from its scope, it is intended that all mattercontained in the above description shall be interpreted as illustrativeand not in a limiting sense. x

It is also to be understood that the followin claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention, which as amatter of language might be said to fall therebetween; and that they areintended to be inclusive in scope and not exclusive, in that, ifdesired, other materials may be added to my novel composition of matterherein claimed without departing from the spirit of the invention.Particularly it is to be understood that in said claims, ingredients orcomponents recited in the singular are intended to include compatiblemixtures of said ingredients where- -ever the sense permits.

Having thus described my invention, what I claim and desire to protectby Letters Patent is: 1. The method comprising heating above about 140F. a mass of a normally liquid unsaturated organic product capable atelevated temperatures of forming a solution with solid polyvinylchloride which solution on cooling is a gel at 70 F. and while said massis in said heated condition, agitating said mass in the presence of a,tree oxygen containing gas until the viscosity of said mass at 25C. hasincreased at least 50% and the combined oxygen content has increased atleast 0.5% and said mass of increased'viscosity and combined oxygencontent is capable at elevated temperatures of forming a solution withsolid polyvinyl chloride which solution on cooling is a gel at 70 F.,said normally liquid unsaturated organic product being an organiccondensation reaction product of formaldehyde and a liquid selected fromthe group consisting of terpenes and terpene alcohols in the presence ofan acidic condensing agent.

2. The method comprising heating above about 140 F. a mass oi? anormally liquid unsaturated organic product capable at elevatedtemperatures 01' forming a solution with solid polyvinyl chloride whichsolution on cooling is a gel at 70 F. and while said mass is in saidheated condition, agitating said mass in the presence of a free oxygencontaining gas until the viscosity of said mass at 25 C. has increasedat least 100% and the combined oxygen content has increased at least0.5% and said mass of increased viscosity and-combined oxygen content iscapable at elevated temperatures of forming a solution with solidpolyvinyl chloride which solution on cooling is a gel at 70 F., saidnormally liquid unsaturated organic product being an organic conden-'sation reaction product of formaldehyde and a liquid selectedirom thegroup consisting of terpenes and terpene alcohols in the presence of aacidic condensing agent. 7 r

3. The method comprising heating between about 140 F. and-about 400 F. amass or a norreaction product of formaldehyde and a. liquid.

selected from the group consisting of terpenes and terpene alcohols inthelpresence of an-acidic condensing agent. v

4. The method comprising heating between about 140 F. and about 400 F. amass or a normally liquid unsaturated organic product capable atelevated temperatures of forming a solution with solid polyvinylchloride which solution on cooling is a gel at F. and while said mass isin said heated condition, agitating said mass in the presence of a freeoxygen containing gas until the viscosity of said mass. at 25 C. hasincreased at least said normally liquid unsaturated organic productbeing an organic condensation reaction product ofiormaldehyde and aliquid selected from the group consisting of terpenes and terpenealcohols in the presence of an acidic condensing agent.

5. The method comprising heating above F. a mass of a normallyliquidorganic condensation product produced by reacting a terpene andformaldehyde in the presence of an acidic agent and being capable atelevated temperatures of forming a solution with solid polyvinylchloride which solution on cooling is a gel at 70 F. and while said massis in said heated condition, agitating said mass in the presence of afree oxygen containing gas until the viscosity of said mass at 25 C. hasincreased at least 50% and the combined oxygen content has increased atleast 0.5% and said mass of increased viscosity and combined oxygencontent is capable at elevated temperatures of forming a solution withsolid polyvinyl chloride which solution on cooling is a gel at 70 F.

' 6. The method comprising heating above 140 F. a mass of a normallyliquid organic condensation product produced by reacting a terpenealcohol and formaldehyde in the presence of an acidic agent and beingcapable at elevated temperatures of forming a solution with solidpolyvinyl chloride which, solution on cooling is a gel at 70 F. andwhile said mass is in said heated condition, agitating said mass in thepresence of a free oxygen containing gas until the viscosity of saidmass at 25 C. has increased at least 50% and the combined oxygenjcontenthas increased at least 0.5% and said mass of increased viscosity andcombined oxygen content is capable at elevated temperatures of forming asolution with solid polyvinyl chloride which solution on cooling is agel-at 70-F.

7. The method'comprising heating above 140 F. a mass of -a normallyliquid organic condensation product produced by reacting turpentine andformaldehyde in the presence of an acidic agent and being capable atelevated temperatures of forming a-solution with solid polyvinylchloride'which solution on cooling is a gel at 70 F. and while said massis in said heated condition,

agitating said mass in the presence or a tree oxygen containing gasuntil the viscosity of said mass at 25 C. has increased at least 50% andthe combined oxygen content has increased at least 0.5% and said mass ofincreased viscosity and combined oxygen content is capable at elevatedtemperatures of forming a solution with solid polyvinyl chloride whichsolution on cooling is a gel at 70 F.

8. The method comprising heating above 140 F. a mass of a normallyliquid organic condensation product produced by reacting pine oil andformaldehyde in the presence of an acidic agent and being capable atelevated temperatures of forming a solution with solid polyvinylchloride which solution on cooling is a gel at 70 F. and while said massis in said heated condition, agitating said mass in the presence of afree oxygen containing gas until the viscosity of said mass T at 25 C.has increased at least 50% and the combined oxygen content has increasedat least 0.5% and said mass of increased viscosity and combined oxygencontent is capable at elevated temperatures of forming a solution withsolid polyvinyl chloride which solution on cooling is a gel at 70 F.

9. The product produced according to the method of claim 1.

10. The product produced according to the method of claim 4.

11. The product produced according to the method of claim 5.

12. The product produced according to the method of claim 6.

13. The product Produced according to the method of claim '7.

14. The product produced according to the method of claim 8.

MORTIMER T. HARVEY.

REFERENCES CITED The following references are of record in the file'ofthis patent:

UNITED STATES PATENTS Number Name Date 1,893,982 Bradley Jan. 10, 19332,265,161 Hasselstrom Dec. 9, 1941 1,929,453 Semon Oct. 10, 1933 FOREIGNPATENTS Number Country Date 8,590 British of year 1905 148,944 GermanFeb. 29, 1904 175,633 German Oct. 11, 1906 OTHER REFERENCES Ellis,Chemistry of Petroleum Derivatives", vol. 1 pp. 925-926 (1934) Copy inDivision 6.

